Crosslinked, water-soluble or water-dispersible polyurethanes

ABSTRACT

The present invention relates to crosslinked, water-soluble or water-dispersible polyurethanes of 
     A) at least one water-soluble or water-dispersible polyurethane prepolymer having terminal isocyanate groups of 
     a) at least one compound having a molecular weight in the range from 56 to 300 which contains two active hydrogen atoms per molecule, 
     b) at least one polymer containing two active hydrogen atoms per molecule, 
     c) at least one compound which contains two active hydrogen atoms and at least one ionogenic or ionic group per molecule, 
     d) at least one diisocyanate, 
     B) at least one polymer containing groups which are reactive toward isocyanate groups, chosen from hydroxyl, and primary and secondary amino and/or carboxyl groups, 
     or the salts thereof.

This is a divisional of Ser. No. 04/303,426, filed May 3, 1999 andissued as U.S. Pat. No. 6,262,176.

The present invention relates to crosslinked, water-soluble orwater-dispersible polyurethanes of at least one polyurethane prepolymercontaining terminal isocyanate groups and at least one polymercontaining groups which are reactive toward isocyanate groups, chosenfrom hydroxyl, and primary and secondary amino- and/or carboxyl groups.

In cosmetics, polymers with film-forming properties are used forsetting, shaping and improving the structure of the hair. These hairtreatment compositions generally contain a solution of the film formerin an alcohol or in a mixture of alcohol and water.

Hairsetting compositions are generally sprayed on the hair in the formof aqueous-alcoholic solutions. Following the evaporation of thesolvent, the individual hairs are held in the desired shape at theirpoints of mutual contact by the polymer which is left behind. Thepolymers should on the one hand be sufficiently hydrophilic that theycan be washed out of the hair, yet on the other hand should behydrophobic so that the hair treated with the polymers retains its shapeeven under conditions of high atmospheric humidity, and the individualhairs do not stick to one another. In order to obtain a highly efficienthairsetting effect, moreover, it is also desirable to employ polymerswhich have a relatively high molecular weight and a relatively highglass transition temperature (at least 15° C.).

A further consideration when formulating hairsetting agents is thatbecause of the environmental regulations governing the emission ofvolatile organic compounds (VOCs) into the atmosphere it is necessary toreduce the content of alcohol and of propellant.

A further current demand on hair treatment compositions is that theyshould give the hair a natural appearance and luster even, for example,when the hair concerned is by its very nature particularly strong and/ordark.

DE-A-42 25 045 and WO 94/03515 describe uncrosslinked, water-soluble orwater-dispersible polyurethanes which comprise, in copolymerized form,at least 5 mol % of a polycondensate of lactic acid and a polyol, andalso the use of water-soluble or water-dispersible polyurethanes of

a) at least one compound which contains two or more active hydrogenatoms per molecule,

b) at least one diol containing acid or salt groups and

c) at least one diisocyanate,

as auxiliary in cosmetic and pharmaceutical preparations.

DE-A-42 41 118 describes the use of uncrosslinked, cationicpolyurethanes and polyureas as auxiliaries in cosmetic andpharmaceutical preparations.

EP-A-619 111 describes the use of polyurethanes based on organicdiisocyanates, diols and 2,2-hydroxymethyl-substituted carboxylates ofthe formula

where A is a hydrogen atom or a C₁-C₂₀-alkyl group in hair fixatives. Inthis case at least some of the carboxyl groups are neutralized with anorganic or inorganic base. Films based on these linear polyurethaneshave little flexibility and are thus in need of improvement.

EP-A-636 361 describes a cosmetic composition comprising, in acosmetically compatible vehicle, at least one pseudolatex based on apolycondensate which comprises at least one polysiloxane unit and atleast one polyurethane and/or polyurea unit having anionic or cationicgroups. Crosslinked, water-soluble or water-dispersible polyurethanesare not described. The disclosure content of WO 97/25021 is similar.These cosmetic compositions are suitable, inter alia, for treatingkeratinous materials. The ease of washout of these film formers,however, is unsatisfactory. In addition, their high siloxane contentrobs them of the setting effect also required of a hair polymer.

DE-A-195 41 329 and WO 97/17052 describe hair treatment compositionscomprising a salt which is dispersible or soluble in water and has theformula I

 [A—(X)_(n)]^(n−).[H_(m)B]^(m+)  I

where

A is a cosmetically acceptable aliphatic, cycloaliphatic or aromaticradical, which may have siloxane-containing units and/orfluorine-containing units,

X is a carboxylate, sulfonate, phosphate or phosphonate group;

B is a cosmetically acceptable amine base which may comprisesiloxane-containing and/or fluorine-containing units;

n is from 1 to 30; and

m is the valence of the amine B.

Hairspray formulations based on these siloxane-containing salts, lead tofilms which are easily removed from the surface of the hair bymechanical stress, for example. The setting effect of these formulationsis therefore in need of improvement.

DE-A-195 41 326 and WO 97/17386 describe water-soluble orwater-dispersible polyurethanes having terminal acid groups, theirpreparation and their use. In this case a polyurethane prepolymer whichis dispersible or soluble in water and has terminal isocyanate groups isreacted with an aminosulfonic or aminocarboxylic acid, especiallytaurine, aspartic acid and glutamic acid. Hair-sprays based on thesepolyurethanes are still in need of improvement. Problems may occur inparticular when formulating hair-sprays having a high content ofpropellant gas and/or a high content of organic solvents and, ifappropriate, with the simultaneous use of spray atomizers for obtainingvery small droplets.

EP-A-0 389 386 describes linear diorganopolysiloxane-polyester blockcopolymers containing incorporated urethane units, which are suitablefor the controlled release of pharmaceutical preparations.

EP-A-0 626 432 describes thermally curable coating compositions of apolyester oligomer-polyacrylate containing free OH groups and at leastone polyisocyanate containing free NCO groups, and their use for thepreparation of clearcoats. Once crosslinked, these polymers are neitherwater-soluble nor water-dispersible and are unsuitable for thepreparation of cosmetic preparations.

WO 97/00664 describes an aqueous nail polish comprising a bifunctionalurethane acrylate oligomer crosslinked with an acrylic resin.Polyurethanes of at least one polyurethane prepolymer containingterminal isocyanate groups are not described. The films resulting fromthese compositions are water-resistant and not redispersible. They arenot suitable for use in cosmetic compositions for use on skin or hair.

EP-A-0 687 459 describes hair treatment compositions based on an aqueouspolymer dispersion obtainable by free-radical graft copolymerization ofa monoethylenically unsaturated siloxane macromonomer and at least onepolyurethane and/or polyurea copolymer. Crosslinked polyurethanes ofpolyurethane prepolymers containing terminal isocyanate groups andpolymers containing groups which are reactive toward isocyanate groupsare not described in this document.

U.S. Pat. No. 3,927,199 describes a hairsetting composition based on acopolymer comprising, in copolymerized form, (1) from 30 to 60% byweight of an N—(C₂- to C₁₂)-alkyl (meth)acrylamide, (2) from 12 to 18%by weight of an α,β-ethylenically unsaturated acid-group-containingcomonomer, (3) from 20 to 55% by weight of at least one comonomer chosenfrom alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, vinyl acetate,vinyl propionate, diacetone acrylamide, styrene and α-methylstyrene.Neutralization with a base gives a copolymer which is water-soluble or-dispersible and is suitable for formulating hair sprays. Crosslinkedpolyurethanes based on polyurethane prepolymers containing terminalisocyanate groups are not described in this document. These hairsettingcompositions exhibit a sharp increase in viscosity in aqueousformulations with increasing water content and are unsuitable for thepreparation of products having a low content of VOC.

WO 97/23519 describes anionic amino-containing polymers obtainable byfree-radical polymerization of olefinic amino-containing monomers in anaqueous medium in the presence of an azo initiator. The initiator hasneutralized carboxyl groups. The amino-containing monomers are, forexample, amino (meth)acrylates, such as tert-butylaminoethyl(meth)acrylate. The polymers may further contain olefinicallyunsaturated monomers, such as (meth)acrylic esters and hydroxyalkyl(meth)acrylates, in copolymerized form. They are suitable for thepreparation of single- or two-component coating compositions, for thecoating of metallic and plastic surfaces, which are cured bycrosslinking with polyisocyanates or polyepoxides. Crosslinked,water-soluble or water-dispersible polymers which are suitable for useas or in a cosmetic composition are not described. Polymers whichcontain, in copolymerized form, an aminoalkyl (meth)acrylate in anamount of from 0.1 to 10% by weight and their use as intermediates forthe preparation of crosslinked, water-soluble or water-dispersiblepolyurethanes are likewise not described.

WO 97/23527 describes an aqueous single-component coating compositionbased on a polyurea binder comprising a polymer containing primaryand/or secondary amino groups which are reactive toward isocyanategroups and which may additionally have hydroxyl groups, and apolyisocyanate. The amino-containing polymers comprise, in copolymerizedform, (1) at least one olefinically unsaturated monomer containingprimary or secondary amino groups, e.g. an aminoalkyl (meth)acrylate,(2) optionally a hydroxyl-containing monomer, e.g. a hydroxyalklyl(meth)acrylate, (3) optionally other olefinically unsaturated monomers,chosen from (meth)acrylic esters, styrene, alkylstyrenes,(meth)acrylonitrile, vinyl acetate etc. The binders which result fromcrosslinking with the polyurethane are suitable for coating metallic andplastic surfaces. Crosslinked, water-soluble or water-dispersiblepolyurethanes are not described. Polymers comprising, in copolymerizedform, from 0.1 to 10% by weight of at least one monomer containing aprimary and/or secondary amino group and their use as intermediates forthe preparation of crosslinked, water-soluble or water-dispersiblepolyurethanes are likewise not described.

U.S. Pat. No. 5,612,404 has a disclosure content corresponding to WO97/23519 and WO 97/23527.

WO 96/30425 describes an aqueous two-component polyisocyanate coatingcomposition based on an essentially isocyanate-free emulsifier,comprising a reaction product of: (1) an isocyanate and (2) a componentchosen from hydroxyl-containing polyalkyl ethers containing at least 5ethylene oxide units, including various alcohols, amino compounds andmixtures thereof. The binders containing groups reactive towardisocyanate groups may be the polymers based on amino alkyl(meth)acrylates described in WO 97/23527.

WO 97/22632 describes a process for the preparation of an adhesivecomposition comprising:

(a) reacting a diol or polyol with a diisocyanate to give a prepolymercontaining terminal isocyanate groups;

(b) reacting the first prepolymer to convert at least some of theterminal isocyanate groups into terminal methacrylate groups, e.g. withan aminoalkyl (meth)acrylate, such as N-tert-butylaminoethylmethacrylate;

(c) reacting the residual isocyanate groups with a stopper, preferablyan alkanolamine, such as triethanolamine;

(d) thermal or photochemical curing of the prepolymer from (c) to form apolyurethane (meth)acrylate-based adhesive. The resulting adhesives arepressure-sensitive and are suitable for use on the skin, e.g. in medicalproducts for the dressing of wounds.

Crosslinked, water-soluble or water-dispersible polyurethanes of apolyurethane prepolymer and a polymer containing groups reactive towardisocyanate groups are not described in this document.

EP-A-0 773 246 describes water-soluble or water-dispersible graftpolymers of

A) a water-soluble or -dispersible polyurethane prepolymer containingterminal isocyanate groups and

B) a protein containing free amino groups.

These are suitable as auxiliaries in cosmetics and, in particular, ashairsetting agents with improved washout. A disadvantage with usingproteins is that they require stabilization by preservatives and, beingnatural substances, frequently have fluctuating product properties.

It is an object of the present invention to provide novel polyurethanes,in particular for hair treatment compositions, which, on the one hand,can be used as hairsetting agent, but on the other hand, also have goodwashout (redispersibility). They should preferably form smooth andflexible films.

Surprisingly, we have found that this object is achieved by crosslinked,water-soluble or water-dispersible polyurethanes which are the reactionproduct of at least one polyurethane prepolymer containing terminalisocyanate groups and at least one polymer containing groups which arereactive toward isocyanate groups.

The present invention thus provides crosslinked, water-soluble orwater-dispersible polyurethanes of

A) at least one water-soluble or water-dispersible polyurethaneprepolymer containing terminal isocyanate groups of

a) at least one compound having a molecular weight in the range from 56to 300 which contains two active hydrogen atoms per molecule,

b) at least one polymer containing two active hydrogen atoms permolecule,

c) at least one compound which contains two active hydrogen atoms and atleast one ionogenic or ionic group per molecule,

d) at least one diisocyanate,

B) at least one polymer containing groups which are reactive towardisocyanate groups, chosen from hydroxyl, and primary and secondary aminoand/or carboxyl groups,

or the salts thereof.

Component a) is preferably a diol, diamine, aminoalcohol, or a mixturethereof. The molecular weight of these compounds is preferably in arange from about 56 to 280. If desired, up to 3 mol % of said compoundscan be replaced by triols or triamines.

Diols are preferably used as component a). Diols which can be used are,for example, ethylene glycol, propylene glycol, butylene glycol,neopentyl glycol, cyclohexanedimethylol, di-, tri-, tetra-, penta- orhexaethylene glycol and mixtures thereof. Preference is given toneopentyl glycol and/or cyclohexanedimethylol.

Suitable aminoalcohols are, for example, 2-aminoethanol,2-(N-methylamino)ethanol, 3-aminopropanol, 4-aminobutanol,1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol,4-methyl-4-aminopentan-2-ol etc.

Suitable diamines are, for example, ethylenediamine, propylenediamine,1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane, andα,ω-diamino polyethers which can be prepared by amination ofpolyalkylene oxides with ammonia.

Component b) is preferably a polymer having a number-average molecularweight in the range from about 300 to 5000, preferably from about 400 to4000, in particular from 500 to 3000. Polymers b) which may be used are,for example, polyesterdiols, polyetherols and mixtures thereof.Polyetherols are preferably polyalkylene glycols, for examplepolyethylene glycols, polypropylene glycols, polytetrahydrofurans etc.,block copolymers of ethylene oxide and propylene oxide or blockcopolymers of ethylene oxide, propylene oxide and butylene oxide whichcontain, in copolymerized form, the alkylene oxide units in randomdistribution or in the form of blocks. Component b) is preferably apolytetrahydrofuran, polyesterdiol or mixture thereof.

Suitable polytetrahydrofurans b) can be prepared by cationicpolymerization of tetrahydrofuran in the presence of acidic catalysts,such as, for example, sulfuric acid or fluorosulfuric acid. Suchpreparation processes are known to the person skilled in the art.

Polyesterdiols b) which can be used preferably have a number-averagemolecular weight in the range from about 400 to 5000, preferably from500 to 3000, in particular, from 600 to 2000.

Suitable polyesterdiols are all those which are. normally employed toprepare polyurethanes, especially those based on aromatic dicarboxylicacids, such as terephthalic, isophthalic, phthalic, Na—orK-sulfoisophthalic acid, etc., on aliphatic dicarboxylic acids, such asadipic or succinic acid, etc., and on cycloaliphatic dicarboxylic acids,such as 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid. Particularlysuitable diols are aliphatic diols, such as ethylene glycol, propyleneglycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol,polyethylene glycols, polypropylene glycols, 1,4-dimethylolcyclohexane,and also poly(meth)acrylatediols of the formula

where R¹⁰ is H or CH₃ and R¹¹ is C₁-C₁₈-alkyl (especially C₁-C₁₂- orC₁-C₈-alkyl) which have a molecular mass of up to about 3000. Diols ofthis kind can be prepared by conventional means and are obtainablecommercially (Tegomer® grades MD, BD and OD from Goldschmidt).

Preference is given to polyesterdiols based on aromatic and aliphaticdicarboxylic acids and aliphatic diols, especially those in which thearomatic dicarboxylic acid accounts for from 10 to 95 mol-%, inparticular from 40 to 90 mol-% and, preferably, from 50 to 85 mol-% ofthe overall dicarboxylic acid component (the remainder being aliphaticdicarbbxylic acids).

Particularly preferred polyesterdiols are the reaction products ofphthalic acid/diethylene glycol, isophthalic acid/1,4-butanediol,isophthalic acid/adipic acid/1,6-hexanediol, 5-NaSO₃-isophthalicacid/phthalic acid/adipic acid/1,6-hexanediol, adipic acid/ethyleneglycol, isophthalic acid/adipic acid/neopentyl glycol, isophthalicacid/adipic acid/neopentyl glycol/diethyleneglycol/dimethylolcyclohexane, and 5-NaSO₃-isophthalic acid/isophthalicacid/adipic acid/neopentyl glycol/diethyleneglycol/dimethylolcyclohexane.

Suitable compounds c), which contain two active hydrogen atoms and atleast one ionogenic or ionic group per molecule, are, for example,compounds having carboxylate and/or sulfonate groups. Particularpreference is given as component c) to dimethylolpropanoic acid andmixtures comprising it.

Suitable diamines and/or diols c) containing ionogenic or ionic groupsare, for example, dimethylolpropanoic acid and compounds of the formula

in which R is in each case a C₂-C₁₈-alkylene group, and Me is Na or K.

As component c) it is also possible to use compounds of the formula

H₂N(CH₂)_(n)—NH—(CH₂)_(m)—COO⁻M⁺

H₂N(CH₂)_(n)—NH—(CH₂)_(m)—SO₃ ⁻M⁺

where m and n independently of one another are an integer from 1 to 8,in particular from 1 to 6, and M is Li, Na or K, and compounds of theformula

H₂N(CH₂CH₂O)_(p)(CH₂CH(CH₃)O)_(q)(CH₂)_(n)—NH—(CH₂)_(m)—SO₃ ⁻M⁺

where m, n and M are as defined above, p and q independently of oneanother are an integer from 0 to 50, at least one of the two variables por q being >0. The order of alkylene oxide units is arbitrary. Thelast-named compounds preferably have a number-average molecular weightin the range from about 400 to 3000.

If compounds having nitrogen-containing groups are used as component c),cationic polyurethanes are obtained. Components c) which can be usedare, for example, compounds of the general formulae

in which

R¹ and R², which may be identical or different, are C₂-C₈-alkylene,

R³, R⁶ and R⁷, which may be identical or different, are C₁-C₆-alkyl,phenyl or phenyl-C₁-C₄-alkyl,

R⁴ and R⁵, which may be identical or different, are H or C₁-C₆-alkyl,

o is 1, 2 or 3,

X⁻ is chloride, bromide, iodide, C₁-C₆-alkylsulfate or SO₄ ²⁻/₂.Particular preference is given to N—(C₁- to C₆-alkyl)diethanolamines,such as methyldiethanolamine.

Suitable as component c) are also mixtures comprising at least one ofthe abovementioned anionic or anionogenic components and at least one ofthe abovementioned cationic or cationogenic components. Preference isthen given to using mixtures comprising dimethylolpropanoic acid andN-methyldiethanolamine.

Component d) comprises customary aliphatic, cycloaliphatic and/oraromatic diisocyanates, such as tetramethylene diisocyanate,hexamethylene diisocyanate, methylenediphenyl diisocyanate, 2,4- and2,6-tolylene diisocyanate and isomer mixtures thereof, o- and m-xylylenediisocyanate, 1,5-naphthylene diisocyanate, 1,4-cyclohexylenediisocyanate, dicyclohexylmethane diisocyanate and mixtures thereof,especially isophorone diisocyanate and/or dicyclohexylmethanediisocyanate. If desired, up to 3 mol % of these compounds may bereplaced by triisocyanates.

The polyurethane prepolymers A) are prepared by reacting the compoundsof components a), b) and, where appropriate, c) with component d). Thetemperature is in a range from about 60 to 140° C., preferably fromabout 70 to 100° C. The reaction can be carried out without solvent orin a suitable inert solvent or solvent mixture. Suitable solvents areaprotic polar solvents, e.g. tetrahydrofuran, ethyl acetate,N-methylpyrrolidone, dimethylformamide and, preferably, ketones, such asacetone and methyl ethyl ketone. The reaction is preferably carried outunder an inert-gas atmosphere, for example under nitrogen. Thecomponents are used in amounts such that the ratio of NCO equivalent ofthe compounds of component d) to equivalent of active hydrogen atom ofcomponents a), b) and, where appropriate, c) is in a range from about1.01:1 to 1.4:1, preferably from 1.03:1 to 1.3:1, in particular from1.05:1 to 1.25:1. The resulting polyurethane prepolymers A) thus stillhave free isocyanate groups.

The polyurethane prepolymers preferably comprise, in copolymerized form,

from 0.3 to 15% by weight, preferably from 0.5 to 12% by weight, of atleast one component a),

from 0.5 to 80% by weight, preferably from 1 to 65% by weight, of atleast one component b),

from 5 to 25% by weight, preferably from 8 to 20% by weight, of at leastone component c),

from 25 to 60% by weight, preferably from 35 to 53% by weight, of atleast one component d).

The crosslinked, water-soluble or water-dispersible polyurethanesaccording to the invention are prepared by reacting at least onepolyurethane prepolymer A), as described above, with at least onepolymer B). The polymers B) comprise, in copolymerized form:

e) at least one α,β-ethylenically unsaturated monomer which additionallycontains at least one group which is reactive toward isocyanate groupsper molecule,

f) optionally at least one α,β-ethylenically unsaturated monomer whichis chosen from esters of α,β-ethylenically unsaturated mono- and/ordicarboxylic acids with C₁- to C₂₂-alkanols, amides of α,β-ethylenicallyunsaturated mono- and/or dicarboxylic acids with mono- and di-C₁- toC₂₂-alkylamines, esters of vinyl alcohol and allyl alcohol with C₁- toC₄₀-monocarboxylic acids, vinyl ethers, aromatic vinyl compounds, vinylhalides, vinylidene halides, C₂- to C₈-monoolefins, nonaromatichydrocarbons having at least 2 conjugated double bonds and mixturesthereof,

g) optionally at least one α,β-ethylenically unsaturated monomer whichis chosen from N-vinylamides, N-vinyllactams, primary amides ofα,β-ethylenically unsaturated monocarboxylic acids, vinyl- andallyl-substituted heteroaromatic compounds and mixtures thereof,

h) optionally at least one further monomer containing a free-radicallypolymerizable, α,β-ethylenically unsaturated double bond and at leastone ionogenic or ionic group per molecule.

Suitable monomers e) are the esters of α,β-ethylenically unsaturatedmono- and dicarboxylic acids, such as acrylic acid, methacrylic acid,fumaric acid, maleic acid, itaconic acid and crotonic acid etc., withC₁-C₂₀-alkanediols. These include, for example, 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropylacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate,3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutylmethacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate,6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate,3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylateetc. Preference is given to hydroxyethyl acrylate and hydroxyethylmethacrylate. Suitable monomers e) are also the esters of theabovementioned acids with triols and polyols, for example glycerol,erythritol, pentaerythritol and sorbitol etc.

Suitable monomers e) are also the esters and amides of theabove-mentioned α,β-ethylenically unsaturated mono- and dicarboxylicacids with C₂- to C₁₂-aminoalcohols which have a primary or secondaryamino group. These include aminoalkyl acrylates and aminoalkylmethacrylates and the N-monoalkyl derivatives thereof which carry, forexample, an N—C₁- to C₈-monoalkyl radical, such as aminomethyl acrylate,aminomethyl methacrylate, aminoethyl acrylate, aminoethyl methacrylate,N-methylaminomethyl acrylate, N-methylaminomethyl methacrylate,N-ethylaminomethyl acrylate, N-ethylaminomethyl methacrylate,N-(n-propyl)aminomethyl (meth)acrylate, N-isopropylaminomethyl(meth)acrylate and, preferably tert-butylaminoethyl acrylate andtert-butylaminoethyl methacrylate. These also include N-(hydroxy-C₁- toC₁₂-alkyl)(meth)acrylamides, such as N-hydroxymethyl(meth)acrylamide,N-hydroxyethyl(meth)acrylamide etc.

Suitable monomers e) are also the amides of the abovementionedα,β-ethylenically unsaturated mono- and dicarboxylic acids with di- andpolyamines which have at least two primary or two secondary or oneprimary and one secondary amino group. These include, for example, thecorresponding amides of acrylic acid and methacrylic acid (referred tobelow by the syllable “(meth)”), such as aminomethyl(meth)acrylamide,aminoethyl(meth)acrylamide, aminopropyl(meth)acrylamide,amino-n-butyl(meth)acrylamide, methylaminoethyl(meth)acrylamide,ethylaminoethyl(meth)acrylamide, methylaminopropyl(meth)acrylamide,ethylaminopropyl(meth)acrylamide and methylamino-n-butyl(meth)acrylamideetc.

Suitable monomers f) are essentially hydrophobic, nonionic monomers.These include the esters of α,β-ethylenically unsaturated mono- anddicarboxylic acids with C₁-C₂₂-alkanols, preferably C₁-C₁₈-alkanols,e.g. the esters of acrylic acid and/or methacrylic acid with methanol,ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol,n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, dodecanol,hexadecanol and octadecanol etc.

Suitable monomers f) are also amides of α,β-ethylenically unsaturatedmono- and dicarboxylic acids with mono- and dialkylamines which havefrom 1 to 22 carbon atoms, preferably from 1 to 18 carbon atoms, peralkyl radical. These include, for example, N—C₁- toC₂₂-alkyl(meth)acrylamides, such as N-methyl(meth)acrylamide,N-ethyl(meth)acrylamide, N-(n-propyl)(meth)acrylamide,N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide,N-(t-butyl)(meth)acrylamide, N-pentyl(meth)acrylamide,N-hexyl(meth)acrylamide, N-heptyl(meth)acrylamide,N-octyl(meth)acrylamide, N-ethylhexyl(meth)acrylamide,N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide etc.

Suitable monomers f) are also vinyl formate, vinyl acetate, vinylpropionate, vinyl-n-butyrate, vinyl stearate, vinyl laurate, styrene,a-methylstyrene, o-chlorostyrene, vinyltoluenes, vinyl chloride,vinylidene chloride, ethylene, propylene, butadiene, isoprene,chloroprene, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether,dodecyl vinyl ether etc.

Suitable monomers g) are essentially hydrophilic, nonionic monomers.These include, for example, N-vinylamides, such as N-vinylformamide,N-vinylacetamide, N-vinylpropionamide etc. Preference is given toN-vinylformamide.

Suitable monomers g) are also N-vinyllactams and derivatives thereofwhich may have, for example, one or more C₁-C₆-alkyl substituents, suchas methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyletc. These include, for example, N-vinylpyrrolidone, N-vinylpiperidone,N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone,N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone,N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam,N-vinyl-7-ethyl-2-caprolactam etc.

Suitable monomers g) are also primary amides of the abovementioned andα,β-ethylenically unsaturated monocarboxylic acids, such as acrylamide,methacrylamide, ethacrylamide etc.

Suitable monomers g) are also vinyl- and allyl-substitutedheteroaromatic compounds, such as 2- and 4-vinylpyridine,-allylpyridine, and preferably N-vinyl heteroaromatic compounds, such asN-vinylimidazole, N-vinyl-2-methylimidazole etc.

The compounds h) have at least one ionogenic or ionic group permolecule, which is preferably chosen from carboxylate groups and/orsulfonate groups and the salts thereof obtainable by partial or completeneutralization with a base, and also tertiary amine groups, which may bepartially or completely protonated and quaternized. Suitable bases forthe neutralization or acids for the protonation and alkylating agentsfor the quaternization are the polyurethanes given below after thepreparation of the polyurethanes according to the invention.

Suitable monomers h) are, for example, the aforementionedα,β-ethylenically unsaturated mono- and/or dicarboxylic acids and theirhalf-esters and anhydrides, such as acrylic acid, methacrylic acid,fumaric acid, maleic acid, itaconic acid, crotonic acid, maleicanhydride, monobutyl maleate etc. Preference is given to acrylic acid,methacrylic acid and alkali metal salts thereof, such as sodium andpotassium salts thereof.

Suitable monomers h) are also acrylamidoalkanesulfonic acids and saltsthereof, such as 2-acrylamido-2-methylpropanesulfonic acid and alkalimetal salts thereof, e.g. sodium and potassium salts thereof.

Other suitable compounds h) are the esters of the abovementionedα,β-ethylenically unsaturated mono- and dicarboxylic acids with C₂- toC₁₂-aminoalcohols which are C₁- to C₈-dialkylated in the amine nitrogen.These include, for example, N,N-dimethylaminomethyl (meth)acrylate,N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate,N,N-diethylaminopropyl (meth)acrylate etc. Preference is given toN,N-dimethylaminopropyl acrylate and N,N-dimethylaminopropyl(meth)acrylate.

Suitable monomers h) are also the amides of the abovementionedα,β-ethylenically unsaturated mono- and dicarboxylic acids with diamineswhich have a tertiary and a primary or secondary amino group. Theseinclude, for example, N-[2-(dimethylamino)ethyl]-acrylamide,N-[2-(dimethylamino)ethyl]methacrylamide,N-[3-(dimethylamino)propyl]acrylamide,N-[3-(dimethylamino)propyl]methacrylamide,N-[4-(dimethylamino)butyl]acrylamide,N-[4-(dimethylamino)-butyl]methacrylamide,N-[2-(diethylamino)ethyl]acrylamide etc.

The polymer B) preferably comprises, in copolymerized form, in additionto component e), at least one component f) and/or g) and, whereappropriate, a component h).

Polymer B) preferably comprises, in copolymerized form,

from 0.05 to 15% by weight, preferably from 0.1 to 10% by weight, of atleast one component e),

from 0 to 99.9% by weight of at least one component f),

from 0 to 99.9% by weight of at least one component g), and

from 0 to 50% by weight, preferably from 0.1 to 46% by weight, of atleast one component h).

The total amount of components f) and g) is preferably in a range from30 to 99.9% by weight, in particular from 40 to 99.5% by weight,especially from 50 to 99.5% by weight.

In a preferred embodiment, the polymer B) comprises, in copolymerizedform,

from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, of atleast one component e)

from 50 to 99.9% by weight, preferably from 60 to 99.5% by weight, of atleast one component g), and

from 0 to 40% by weight, preferably from 0 to 35% by weight, of at leastone component h).

In another preferred embodiment, the polymer B) comprises, incopolymerized form,

from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, of atleast one component e),

from 50 to 99.9% by weight, preferably from 60 to 90% by weight, of atleast one component f), and

from 0 to 50% by weight, preferably from 10 to 46% by weight, of atleast one component h).

In another preferred embodiment, the polymer B) comprises, incopolymerized form,

from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, of atleast one component e),

from 0.1 to 99.9% by weight, preferably from 0.1 to 90% by weight, of atleast one component f),

from 0.1 to 99.9% by weight, preferably from 0.1 to 99.5% by weight, ofat least one component g), and

from 0 to 50% by weight, preferably from 0 to 46% by weight, of at leastone component h).

The invention further provides a polymer B) which comprises, incopolymerized form,

from 0.05 to 15% by weight, preferably from 0.1 to 10% by weight, of acomponent e), as defined in claim 5, preferably tert-butylaminoethylacrylate and/or tert-butylaminoethyl methacrylate,

from 0 to 99.9% by weight of at least one component f),

from 0.1 to 99.9% by weight of at least one component g),

from 0 to 50% by weight, preferably from 0.1 to 46% by weight, of atleast one component h)

where the total amount of components f) and g) is preferably in a rangefrom 30 to 99.9% by weight.

The polymer B) is prepared by customary processes known to the personskilled in the art. These include bulk polymerization and, preferably,solution polymerization. The polymerization temperature is usually from30 to 120° C., preferably from 40 to 100° C. The polymerization mediumcan consist either only of an organic solvent or of mixtures of waterand at least one water-miscible, organic solvent. Preferred organicsolvents are, for example, alcohols, such as methanol, ethanol,n-propanol, isopropanol, n-butanol, ketones, such as acetone and methylethyl ketone, tetrahydrofuran etc. Solution polymerization can either becarried out as a batch process or else in the form of a feed. method,including monomer feed, stepwise and gradient procedure. Preference isgenerally given to the feed method in which, where appropriate, some ofthe polymerization batch is heated to the polymerization temperature andthen the remainder of the polymerization batch is fed to thepolymerization zones, usually via one or also two or more, spatiallyseparated feed lines, continuously, stepwise or with superimposition ofa concentration gradient with maintenance of the polymerization.

Suitable initiators for the free-radical polymerization are azocompounds suitable for the free-radical polymerization. These includealiphatic or cycloaliphatic azo compounds, e.g.2,2′-azobis(isobutyronitrile), 2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile),2-(carbamoylazo)isobutyronitrile, 4,4′-azobis(4-cyanovaleric acid) andalkali metal and ammonium salts thereof, for example the sodium salt,dimethyl-2,2′-azobisisobutyrate,2,2′-azobis[2-(2-imidazolin-2-yl)propane], 2,2′-azobis(2-amidinopropane)and the acid addition salts of the last two compounds, e.g. thedihydrochlorides.

Other suitable initiators are hydrogen peroxide, hydroperoxides incombination with reducing agents and per salts. Suitable hydroperoxidesare, for example, t-butyl hydroperoxide, t-amyl hydroperoxide, cumenehydroperoxide and pinane hydroperoxide, each in combination with, forexample, a salt of hydroxymethane-sulfinic acid, an iron(II) salt orascorbic acid. Suitable per salts are, in particular, alkali metalperoxydisulfates.

The amount of initiator used, based on the monomers, is generally in arange from about 0.02 to 15 mol %, preferably 0.05 to 3 mol %.

If relatively low molecular weights are desired, these can be set byadding a regulator to the polymerization batch. Suitable regulators are,for example, aldehydes, such as formaldehyde, acetaldehyde,propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid,ammonium formate, hydroxylammonium sulfate and hydroxylammoniumphosphate. Other possible regulators may contain sulfur in organicallybonded form, such as di-n-butyl sulfide, di-n-octyl sulfide, diphenylsulfide, etc., or regulators comprising sulfur in the form of SH groups,such as n-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan.Suitable compounds are also water-soluble, sulfur-containingpolymerization regulators, for example hydrogen sulfites and disulfites.Further suitable regulators are allyl compounds, such as allyl alcoholor allyl bromide, benzyl compounds, such as benzyl chloride or alkylhalides, such as chloroform or tetrachloromethane.

If desired, one or more polymerization initiators are added to thepolymer solution following the polymerization reaction, and the polymersolution is heated, for example to the polymerization temperature or totemperatures above the polymerization temperature, in order to completethe polymerization. Suitable compounds are the azo initiators givenabove, and also all other customary initiators suitable for free-radicalpolymerization in aqueous solution, for example, peroxides,hydroperoxides, peroxodisulfates, percarbonates, peroxo esters andhydrogen peroxide. As a result, the polymerization reaction achieves ahigher conversion, for example of 99.9%. The solutions which form duringthe polymerization can, where appropriate, be converted into solidpowders by a prior art drying process. Preferred processes are, forexample, spray-drying, spray fluidized-bed drying, roller-drying andbelt-drying. Freeze-drying and freeze concentration can also be used. Ifdesired, some or all of the solvent can be removed by customary methods,e.g. distillation at reduced pressure, and, where appropriate, bereplaced by the solvent used for the subsequent reaction of polymer B)with the polyurethane prepolymer A). Hydroxyl-containing polymers B),which have been prepared in a solvent having active hydrogen atoms, arepreferably dried prior to reaction with A), and then used in a solventor solvent mixture which does not have any active hydrogen atoms.

The polyurethanes according to the invention are prepared by reactingthe polyurethane prepolymer A) with the polymer B). The ratio of NCOequivalent of component A) to equivalent active hydrogen atom ofcomponent B) is generally in a range from about 20:1 to 1:1, preferablyfrom 10:1 to 1:1, in particular from 10:1 to 1.01:1. The temperature ofthe reaction is generally in a range from about 10 to 150° C.,preferably from about 20 to 90° C. The reaction can advantageously becarried out in a suitable inert solvent or solvent mixture. Suitablesolvents are those specified above for the preparation of thepolyurethane prepolymers A). If component B) is a hydroxyl-containingpolymer, then the reaction temperature is preferably in a range fromabout 60 to 150° C. The reaction is then preferably carried out asolvent or solvent mixture which does not have any active hydrogenatoms. Preference is given to ketones, such as acetone, methyl ethylketone and mixtures thereof. If component B) is a polymer having largelyor exclusively primary and/or secondary amino groups as groups which arereactive towards isocyanate groups, then the reaction temperature ispreferably in a range from about 20 to 80° C. The reaction can then, ifdesired, be carried out in a solvent or solvent mixture which may haveactive hydrogen atoms. In addition to the substances mentioned above,preference is given to using alcohols, such as methanol and ethanol,mixtures of alcohols and water and also mixtures of alcohols and theabovementioned ketones. The polyurethanes according to the invention arepreferably prepared by introducing initially a solution of one of thecomponents A) or B) into a customary reactor known to the person skilledin the art, e.g. a stirred reactor. The second component is thenpreferably likewise added in the form of a solution, and when additionis complete, the reaction is continued until the NCO content of themixture remains constant. If the resulting polyurethanes still have freeisocyanate groups, the latter are finally inactivated by adding amines,preferably aminoalcohols. Suitable aminoalcohols are those describedabove, preferably 2-amino-2-methyl-1-propanol.

The polyurethanes containing acid groups can be neutralized partially orcompletely using a base.

As a rule, the resulting salts of the polyurethanes have bettersolubility in water or dispersibility in water than the unneutralizedpolyurethanes. Suitable bases for the neutralization of thepolyurethanes are alkali metal bases, such as sodium hydroxide solution,potassium hydroxide solution, soda, sodium hydrogencarbonate, potassiumcarbonate or potassium hydrogencarbonate and alkaline earth metal bases,such as calcium hydroxide, calcium oxide, magnesium hydroxide ormagnesium carbonate, and ammonia and amines. Suitable amines are, forexample C₁-C₆-alkylamines, preferably n-propylamine and n-butylamine,dialkylamines, preferably diethylpropylamine and dipropylmethylamine,trialkylamines, preferably triethylamine and triisopropylamine,C₁-C₆-alkyldiethanolamines, preferably methyl- or ethyldiethanolamineand di-C₁-C₆-alkylethanolamines. Particularly for use in hair treatmentcompositions, 2-amino-2-methyl-1-propanol, diethylaminopropylamine andtriisopropanolamine have proven successful for the neutralization of theacid-containing polyurethanes. If desired, it is also possible to use asiloxane-containing amine for the neutralization, preferably amonoamine, e.g. 3-aminopropyltrimethoxysilane. Neutralization of theacid-containing polyurethanes can also be carried out using mixtures oftwo or more bases, e.g. mixtures of sodium hydroxide solution andtriisopropanolamine. Depending on the intended use, neutralization canbe partial, e.g. up to 20 to 40%, or complete, i.e. up to 100%.

The polyurethanes containing amino groups or protonated or quaternizedamino groups are, because of their cationic groups, generally readilysoluble in water or water/alcohol mixtures, or at least dispersiblewithout the aid of emulsifiers. Charged cationic groups can be producedfrom the present tertiary amine nitrogens either by protonation, e.g.using carboxylic acids, such as lactic acid, or mineral acids, such asphosphoric acid, sulfuric acid and hydrochloric acid, or byquaternization, e.g. using alkylating agents, such as C₁- to C₄-alkylhalides or sulfates. Examples of such alkylating agents are ethylchloride, ethyl bromide, methyl chloride, methyl bromide, dimethylsulfate and diethyl sulfate.

In a suitable embodiment, the polyurethanes according to the inventioncan have both acid groups and amino groups. The difference in the numberof acid groups and the number of amino groups (|ΔSZ-AZ|) is preferablyin a range from about 15 to 150, preferably from 30 to 100. Acid numberand amine number are in each case defined as mg of KOH/g of testsubstance.

If, in the preparation of the polyurethanes, a water-miscible organicsolvent is used, the latter can be subsequently removed by customaryprocesses known to the person skilled in the art, e.g. by distillationat reduced pressure. Prior to removal of the solvent, water canadditionally be added to the polyurethane. Replacement of the solvent bywater gives a solution or dispersion of the polymer, from which, ifdesired, the polymer can be obtained in the usual manner, e.g. byspray-drying.

The polyurethanes according to the invention do not have any siloxanegroups. Their K values (measured in accordance with E. Fikentscher,Cellulose-Chemie 13 (1932), p. 58-64, on a 1% strength solution inN-methylpyrrolidone) are generally in a range from about 15 to 90,preferably from 20 to 60. Their glass transition temperature isgenerally at least 0° C., preferably at least 20° C., particularlypreferably at least 25° C. and especially at least 30° C. if thepolyurethanes according to the invention have two or more glasstransition temperatures, then at least one of them is in the statedrange. The other(s) is/are then preferably below the temperature rangegiven above.

The polyurethanes according to the invention can be used as auxiliariesin cosmetics and pharmacy, in particular as or in coating composition(s)for keratinous surfaces (hair, skin and nails) and as coatingcompositions and/or binders for solid medicaments. In addition, they canbe used as or in coating composition(s) for the textile, paper,printing, leather and adhesives industries. In particular, they can beused in hair cosmetics. The abovementioned polyurethanes can also beused in creams and as tablet coatings and tablet binders. They are alsosuitable as binders and adhesives for cosmetic products, e.g. in thepreparation of stick-shaped cosmetic products, such as deodorant sticks,and makeup sticks etc.

The present invention also provides a cosmetic or pharmaceuticalcomposition which comprises the polyurethanes according to theinvention. The composition generally comprises the polyurethanes in anamount in the range from 0.2 to 30% by weight, based on the overallweight of the composition.

The cosmetic compositions according to the invention are particularlysuitable as compositions for coating keratinous surfaces (hair, skin andnails). The compounds employed therein are water-soluble orwater-dispersible. Where the compounds employed in the compositionsaccording to the invention are dispersible in water, they can be appliedin the form of aqueous microdispersions having particle diameters ofusually from 1 to 250 nm, preferably from 1 to 500 nm. In this case. thesolids contents of the preparations are usually within a range fromabout 0.5 to 20% by weight, preferably from 1 to 12% by weight. Ingeneral, such microdispersions do not require stabilization byemulsifiers or surfactants.

With preference, the compositions according to the invention can be inthe form of a hair treatment composition, especially in the form of ahairspray. For use as hairsetting agents, preferred compositions arethose comprising polyurethanes whose glass transition temperature T_(g)is at least ≧20° C., preferably ≧30° C. The K value of these polymers ispreferably in a range from 23 to 90, in particular from 25 to 60.

The compositions are preferably hair treatment compositions, and areusually in the form of an aqueous dispersion or in the form of analcoholic or aqueous-alcoholic solution. Examples of suitable alcoholsare ethanol, propanol, isopropanol, etc.

In addition, the hair treatment compositions according to the inventiongenerally comprise customary cosmetic auxiliaries, examples beingsofteners, such as glycerol and glycol; emollients; perfumes; UVabsorbers; colorants; antistatics; combability improvers; preservatives;and antifoams.

When formulated as hairsprays, the novel compositions comprise asufficient amount of a propellant: for example, a low-boilinghydrocarbon or ether, such as propane, butane, isobutane or dimethylether. As propellants it is also possible to use compressed gases, suchas nitrogen, air or carbon dioxide. The amount of propellant can be keptlow so as not unnecessarily to raise the voc content. In general thesaid amount is not more than 55% by weight, based on the overall weightof the composition. However, higher VOC contents of 85% by weight ormore are also possible if desired.

The polyurethanes described above can also be employed in thecompositions in combination with other hair polymers. Such polymers are,in particular:

nonionic, water-soluble or water-dispersible polymers or oligomers, suchas polyvinylcaprolactam, e.g. Luviskol Plus (BASF), orpolyvinylpyrrolidone and its copolymers, especially with vinyl esterssuch as vinyl acetate, e.g. Luviskol VA 37 (BASF); polyamides, forexample those based on itaconic acid and aliphatic diamines;

amphoteric or zwitterionic polymers, such as the octylacrylamide/methylmethacrylate/tert-butylamionoethyl methacrylate/2-hydroxypropylmethacrylate copolymers obtainable under the names Amphomer® (DelftNational), and zwitterionic polymers as disclosed, for example, inGerman Patent Applications DE 39 29 973, DE 21 50 557, DE 28 17 369 andDE 37 08 451. Acrylamidopropyltrimethylammonium chloride/acrylic acidand/or methacrylic acid copolymers, and the alkali metal salts andammonium salts thereof, are preferred zwitterionic polymers. Suitablezwitterionic polymers are also methacryloylethyl betaine/methacrylatecopolymers, which are commercially available under the name Amersette®(AMERCHOL) and copolymers of hydroxyethyl methacrylate, methylmethacrylate, N,N-dimethylaminoethyl methacrylate and acrylic acid(Jordapon®);

anionic polymers, such as vinyl acetate/crotonic acid copolymers, as arecommercially available, for example, under the names Resyn® (NATIONALSTARCH), Luviset® (BASF) and Gafset® (GAF), vinylpyrrolidone/vinylacrylate copolymers, obtainable for example under the trademarkLuviflex® (BASF). A preferred polymer is the vinylpyrrolidone/acrylateterpolymer obtainable under the name Luviflex® VBM-35 (BASF), acrylicacid/ethyl acrylate/N-tert-butylacrylamide terpolymers, which aremarketed, for example, under the name Ultrahold® strong (BASF), andLuvimer® (BASF, terpolymer of t-butyl acrylate, ethyl acrylate andmethacrylic acid), or

cationic (quaternized) polymers, e.g. cationic polyacrylate copolymersbased on N-vinyllactams and derivatives thereof (N-vinylpyrrolidone,N-vinylcaprolactam etc.) and also customary cationic hair conditionerpolymers, e.g. Luviquat® (copolymer of vinylpyrrolidone andvinylimidazolium methochloride), Luviquat Hold (copolymer of quaternizedN-vinylimidazole, N-vinylpyrrolidone and N-vinylcaprolactam), Merquat®(polymer based on dimethyldiallylammonium chloride), Gafquat®(quaternary polymers formed by reacting polyvinylpyrrolidone withquaternary ammonium compounds), polymer JR (hydroxyethylcellulose withcationic groups), polyquaternium types (CTFA names) etc.;

nonionic, siloxane-containing, water-soluble or -dispersible polymers,e.g. polyether siloxanes, such as Tegopren® (Goldschmidt) or Belsil®(Wacker).

The crosslinked polyurethanes according to the invention can be employedas a mixture with another amido-functional hair polymer. Such polymersinclude, for example, the polyurethanes described in DE-A-42 25 045, theabove-described vinylpyrrolidone/acrylate terpolymers and acrylicacid/ethyl acrylate/N-tert-butylacrylamide terpolymers (e.g.Ultrahold®strong from BASF AG), the above-described amido-functionalamphoteric polymers (e.g. Amphomer®) and, in particular, copolymershaving a content of amido-functional monomers, such as N-vinyllactams,of at least 30% by weight (e.g. Luviskol®plus and Luviskol®VA37 fromBASF AG).

The crosslinked polyurethanes according to the invention can also beused as a mixture with another siloxane-containing hair polymer,preferably siloxane-containing polyurethanes.

The other hair polymers are preferably present in amounts of up to 10%by weight, based on the overall weight of the composition.

A preferred hair treatment composition comprises:

a) from 0.5 to 20% by weight of at least one water-soluble or-dispersible polyurethane according to the invention,

b) from 40 to 99% by weight, preferably from 50 to 98% by weight, of asolvent chosen from water and water-miscible solvents, preferably C₂- toC₅ alcohols, in particular ethanol, and mixtures thereof,

c) from 0 to 50% by weight of a propellant, preferably dimethyl ether,

d) from 0 to 15% by weight of at least one water-soluble or -dispersiblehair polymer which is different from a),

e) from 0 to 0.2% by weight of at least one water-insoluble silicone,

f) from 0 to 2% by weight of at least one nonionic, siloxane-containing,water-soluble or -dispersible polymer

and customary additives.

The composition according to the invention may comprise, as componentd), at least one other hair polymer which is dispersible or soluble inwater. The proportion of this component will then in general be fromabout 0.1 to 15% by weight, preferably from 0.1 to 10% by weight, basedon the overall weight of the composition. In this context it is possiblewith preference to employ water-soluble or water-dispersiblepolyurethanes which contain siloxane groups in copolymerized form.

The composition according to the invention may comprise, as componente), at least one water-insoluble silicone, especially apolydimethylsiloxane, e.g. the Abil® grades from Goldschmidt. Theproportion of this component will then in general be from about 0.0001to 0.2% by weight, preferably from 0.001 to 0.1% by weight, based on theoverall weight of the composition.

The composition according to the invention may comprise, as componentf), at least one nonionic, siloxane-containing, water-soluble or-dispersible polymer, chosen in particular from the polyether siloxanesdescribed above. The proportion of this component will then in generalbe from about 0.001 to 2% by weight, based on the overall weight of thecomposition.

The composition according to the invention may additionally comprise, ifdesired, an antifoam based, for example, on silicone. The amount of theantifoam will then in general be up to about 0.001% per weight, based onthe overall amount of the composition.

The compositions according to the invention have the advantage that onthe one hand they give the hair the desired set and on the other handthe polymers are easy to wash out (redispersible). Furthermore, it ispossible to formulate hair treatment compositions with a VOC content ofless than 85% by weight, preferably less than 60% by weight, and also toprepare purely aqueous formulations, even if they are formulated ashairsprays.

The invention is illustrated further by the following non-limitingexamples.

EXAMPLES Examples 1 to 4 Polyurethane Prepolymer Preparation

In a stirred apparatus fitted with stirrer, dropping funnel,thermometer, reflux condenser and equipment for operating undernitrogen, a polyesterdiol (M_(n)=1000 g/mol, prepared from isophthalicacid, adipic acid and hexanediol) (Examples 1 to 3) and/or apolytetrahydrofuran (M_(n)=1000 g/mol) (Examples 3, 4),cyclohexanedimethylol (Example 1) or neopentyl glycol (Examples 2 to 4),dimethylolpropanoic acid and, where appropriate, methyldiethanolamine(Example 4) in an amount in accordance with Table 1 were dissolved inmethyl ethyl ketone (solids content of the resulting reaction solutionabout 75%) with heating to a temperature of about 70° C. and withstirring. Isophorone diisocyanate was then added dropwise with stirringin an amount in accordance with Table 1, during which the reactiontemperature increased. At an internal temperature of 85° C., thereaction mixture was then stirred until the isocyanate content of themixture remained virtually constant (from about 0.5 to 1%). The reactionmixture was diluted to 40% by weight with methyl ethyl ketone and cooledto room temperature with stirring.

TABLE 1 Ex. Polyesterdiol¹⁾ Poly(THF)²⁾ CHDM³⁾ NPG⁴⁾ DMPA⁵⁾ MDEA⁶⁾IPDI⁷⁾ No. [mol] [mol] [mol] [mol] [mol] [mol] [mol] 1 0.8 — 1.7 — 3 — 62 1.2 — — 1.4 3 — 6 3 0.7 0.7 — 1.2 3 — 6 4 — 1   — 1.0 3 0.5 6¹⁾Polyesterdiol of isophthalic acid, adipic acid, hexanediol, M_(n) =1000 g/mol ²⁾Polytetrahydrofuran, M_(n) = 1000 g/mol ³⁾CHDM =Cyclohexanedimethylol ⁴⁾NPG = Neopentyl glycol ⁵⁾DMPA =Dimethylolpropanoic acid ⁶⁾MDEA = N-Methyldiethanolamine ⁷⁾IPDI =Isophorone diisocyanate

Examples 5 to 21 Preparation of Polymer B

Feed 1: 300 g monomer mixture according to Table 2

30 g solvent:

Examples 5, 6, 8-13, 17-21: ethanol

Examples 7, 14-16: ethanol/water (1:1)

Feed 2: 0.6 g 2,2′-azobis(2-methylbutyronitrile)

150 g ethanol

Feed 3: 3.0 g 2,2′-azobis(2-methylbutyronitrile)

150 g ethanol.

In a stirred apparatus fitted with reflux condenser and two separatefeed devices 20% by weight of feed 1 (monomer mixture in accordance withTable 2), 12% by weight of feed 2 and 120 g of ethanol were heated toabout 75° C. After partial polymerization, detectable when the viscositystarts to increase, the remainder of feed 1 was added over the course of4 hours and the remainder of feed 2 over the course of 5 hours, theinternal temperature being maintained at from about 70 to 75° C. Feed 3was then added over the course of 2 hours, the internal temperaturebeing increased to about 80° C. When addition was complete, the mixturewas afterpolymerized for about another 5 hours at this temperature. Theresulting polymers can be used for the polyurethane preparation withoutfurther measures for reducing the residual monomer content. Polymerswith very low residual monomer contents are obtained if, instead of feed3, 2,5-bis-(tert-butylperoxy-2,5-dimethylhexane) (Trigonox® 101 fromAkzo Nobel) in 150 g of ethanol, for example, is added to the reactionmixture over the course of 2 hours, and then the mixture isafterpolymerized for about another 5 hours at a temperature of about130° C. under the autogenous pressure of the reaction mixture.

Following the polymerization, the hydroxyl-containing polymers ofExamples 5 to 8 are dried by spray drying, and then 40% by weightstrength solutions of these polymers in methyl ethyl ketone are preparedfor the subsequent reaction.

In the case of the polymers of Examples 14 to 16 prepared in a solventmixture of ethanol/water (1:1), the solvent is removed by distillationunder reduced pressure at about 40° C., and then 40% by weight strengthsolutions in ethanol are prepared for the subsequent reaction.

The ethanolic solutions of the other polymers are likewise adjusted to40% by weight by adding further ethanol.

TABLE 2 Monomer feed 1 VP¹⁾ VCap²⁾ t.-BA³⁾ EHMA⁴⁾ HEMA⁵⁾ MAS⁷⁾ AMPS-Na⁸⁾DMAPMA⁹⁾ Ex. [% by [% by [% by [% by [% by t.-BAEMA⁶⁾ [% by [% by [% byNo. wt.] wt.] wt.] wt.] wt.] [% by wt.] wt.] wt.] wt.] 5 97 — — — 3 — —— — 6 47 50 — — 3 — — — — 7 37 — 45 — 3 — MAS-Na¹⁰⁾ — — 15 8 47 42 — — 3— — — 8 9 98 — — — — 2 — — — 10 —   99.5 — — —   0.5 — — — 11 — 69 30 —— 1 — — — 12 69 — 30 — — 1 — — — 13 59 — 35 5 — 1 — — — 14 — — 73 — — 225 — — 15 — — 23 30  — 2 — 45 — 16 74 — — — — 1 — 25 — 17 90 — — — — 1 —— 9 18 45 45 — — — 1 — — 9 19 — 90 — — — 1 — — 9 20 —   90.5 — — —   0.5— — 9 21 45 — 35 5 — 1 — — 14  ¹⁾VP = Vinylpyrrolidone ²⁾VCap =Vinylcaprolactam ³⁾t-BA = tert-Butyl acrylate ⁴⁾EHMA = Ethylhexylmethacrylate ⁵⁾HEMA = Hydroxyethyl methacrylate ⁶⁾t-BAEMA =tert-Butylaminoethyl methacrylate ⁷⁾MAS = Methacrylic acid ⁸⁾AMPS-Na =Sodium salt of acrylamidomethylpropanesulfonic acid ⁹⁾DMAPMA =Dimethylaminopropyl methacrylate ¹⁰⁾MAS-Na = Sodium salt of methacrylicacid

Examples 22 to 26 Polyurethane Preparation

In a stirred apparatus fitted with stirrer, dropping funnel, thermometerand reflux condenser a 40% strength by weight solution of a polyurethanepolymer from Example 1 to 3 in methyl ethyl ketone, as given in Table 3,was heated to 60° C. A 40% by weight strength solution of ahydroxyl-containing polymer B) from Example 5 to 8, likewise in methylethyl ketone, in accordance with Table 3 was then mixed in. The reactionmixture was stirred at a temperature of about 85° C. until theisocyanate group content of the mixture remained virtually constant(about 2 hours). Water was then added to the reaction mixture, and thereaction product was neutralized using 2-amino-2-methylpropanol (pHabout 8.0). The methyl ethyl ketone was then distilled off under reducedpressure at 40° C., and an aqueous dispersion of the polyurethane wasobtained.

A pulverulent product can be obtained by spray-drying.

Examples 27 to 41

A stirred apparatus fitted with stirrer, dropping funnel, thermometerand reflux condenser was charged with a 40% by weight strength solutionof a polyurethane prepolymer from Example 1 to 4 in methyl ethyl ketonein accordance with Table 3. At a temperature of about 30° C., a polymerB) in accordance with Table 3 in the form of a 40% by weight strengthsolution in ethanol was then mixed in. The reaction mixture was thenstirred for about 1 hour at the ambient temperature. Water was thenadded to the reaction mixture, and the reaction product was neutralizedusing 2-amino-2-methylpropanol (pH about 8.0). The methyl ethyl ketonewas then distilled off under reduced pressure at 40° C., and an aqueousdispersion of the polyurethane was obtained.

A pulverulent product can be obtained by spray-drying.

TABLE 3 PU prepolymer Polymer B) Ex. Ex. [% by Ex. [% by No. No. weight]No. weight] K value¹⁾ 22 1 80  5 20 33 23 1 50  6 50 37.3 24 1 90  8 1032.4 25 2 90  8 10 34.7 26 3 90  8 10 36.1 27 1 90  9 10 34.7 28 1 70 1030 35.4 29 1 90 14 10 37.6 30 1 80 16 20 39.4 31 1 80 18 20 31.2 32 2 8018 20 32 33 3 80 18 20 35.3 34 1 90 21 10 32.1 35 1 80 21 20 37.4 36 120 21 80 45.2 37 3 50 10 50 42 38 4 50 10 50 38.7 39 4 90 10 10 32.1 404 90 18 10 33.2 41 4 10 14 90 42.8 ¹⁾1% by weight strength solution inN-methylpyrrolidone

The abovedescribed aqueous dispersions of the crosslinked polyurethanesaccording to the invention can be used directly for the preparation ofhairspray formulations.

Application Examples Examples 42 to 61

Aerosol hairspray formulations with a VOC content of 97% by weight:

Polyurethane in accordance 3.00% by weight with Example 22-41 Ethanol62.00% by weight Dimethyl ether 34.96% by weight Perfume, additives q.s.

Examples 62 to 76

Compact aerosol hairspray formulations with a VOC content of 90% byweight:

Polyurethane in accordance 10.00% by weight with Example 22-36 Ethanol55.00% by weight Dimethyl ether 34.96% by weight Perfume, additives q.s.

Examples 77 to 96

Hairspray formulations with a VOC content of 80% by weight:

Polyurethane in accordance 5.00% by weight with Example 22-41 Ethanol45.00% by weight Water 15.00% by weight Dimethyl ether 34.96% by weightPerfume, additives q.s.

Examples 97 to 116

Hairspray formulations with a VOC content of 55% by weight:

Polyurethane in accordance 5.00% by weight with Example 22-41 Ethanol20.00% by weight Water 40.00% by weight Dimethyl ether 34.96% by weightPerfume, additives q.s.

Examples 117 to 136

Pump hairspray formulations with 0 VOC content:

Polyurethane in accordance 10.00% by weight with Example 22-41 Water89.97% by weight Perfume, additives q.s.

We claim:
 1. A crosslinked, water-soluble or water-dispersible polyurethane of A) at least one water-soluble or water-dispersible polyurethane prepolymer containing terminal isocyanate groups of a) at least one compound having a molecular weight in the range from 56 to 300 which contains two active hydrogen atoms per molecule, b) at least on polymer containing two active hydrogen atoms per molecule, c) at least one compound which contains two active hydrogens and at least one ionogenic or ionic group per molecule, d) at least one diisocyanate, B) at least one polymer containing groups which are reactive towards isocyanate groups, chosen from hydroxyl, and primary and secondary amino and/or carboxyl groups, or a salt thereof, where the polymer B) comprises, in copolymerized form, e) at least one α,β-ethylenically unsaturated monomer which additionally contains at least one group which is reactive toward isocyanate groups per molecule, f) optionally at least one α,β-ethylenically unsaturated monomer which is chosen from esters of α,β-ethylenically unsaturated mono- and/or dicarboxylic acids with C₁-C₂₂-alkanols, amides of α,β-ethylenically unsaturated mono- and/or dicarboxylic acids with mono- and di-C₁- to C₂₂-alkylamines, esters of vinyl alcohol and allyl alcohol with C₁- to C₄₀-monocarboxylic acids, vinyl ethers, aromatic vinyl compounds, vinyl halides, vinylidene halides, C₂- to C₈-monoolefins, nonaromatic hydrocarbons having at least 2 conjugated double bonds and mixtures thereof, g) optionally at least one α,β-ethylenically unsaturated monomer which is chosen from N-vinylamides, N-vinyllactams, primary amides of α,β-ethylenically unsaturated monocarboxylic acids, vinyl- and allyl-substituted heteroaromatic compounds and mixtures thereof, h) optionally at least one further monomer containing a free-radically polymerizable, α,β-ethylenically unsaturated double bond and at least one ionogenic group per molecule.
 2. A polyurethane as claimed in claim 1, where the ratio of NCO equivalent of the compounds of component d) to equivalent of active hydrogen atom of components a), b) and c) is in a range from 1.01:1 to 1.4:1.
 3. A polyurethane as claimed in claim 1, where the polymer B) comprises, in copolymerized form, from 0.05 to 15% by weight of at least one component e), from 0 to 99.9% by weight of at least one component f), from 0 to 99.9% by weight of at least one component g), and from 0 to 50% by weight of at least one component h) the total amount of components f) and g) being in a range from 30 to 99.9% by weight.
 4. A polyurethane as claimed in claim 1, where the component e) is an ester of acrylic acid or methacrylic acid with a C₂- to C₁₂-aminoalcohol, where the amine nitrogen may additionally carry a C₁- to C₈-alkyl radical.
 5. A polyurethane as claimed in claim 1 where the ratio of NCO equivalent of the component A) to equivalent of active hydrogen atom of component B) is in a range from 20:1 to 1:1.
 6. A polyurethane as claimed in claim 4 which comprises, in copolymerized form from 0.05 to 15% by weight of a component e), from 0 to 99.9% by weight of at least one component f), from 0.1 to 99.9% by weight of at least one component g), from 0 to 50% by weight of at least one component h) where the total amount of components f) and g) is in a range from 30 to 99.9% by weight.
 7. A coating composition for the textile, paper, printing, leather and adhesives industries, which comprises at least one polyurethane as claimed in claim
 1. 8. A polyurethane as claimed in claim 6 which comprises, in copolymerized form, from 0.05 to 15% by weight of tert-butylaminoethyl acrylate and/or tert-butylaminoethyl methacrylate as component e). 